Haloalkanoyl derivatives of fluorinated amides

ABSTRACT

HALOALKANOYL DERIVATIVES OF FLUORINATED AMIDES USEFUL AS OIL- AND WATER-REPELLENCY AGENTS HAVE THE STRUCTURAL FORMULA   RF-CO-NH-(CXH2X-N(-Z&#39;&#39;))Y-CXH2X-NH-Z   WHEREIN X AND Y ARE INTEGERS FROM 2 TO 6 AND 1 TO 4, RESPECTIVELY; WHEREIN RF IS A PERFLUORALKYL OR A FLUORINATED ISOALKOXYALKYL RADICAL; Z IS H, ALKYL, HYDROXYALKYL, A FLUORINATED ACYL RADICAL RFCO-WHEREIN RF IS AS DESCRIBED ABOVE, OR A HALOALKANOYL RADICAL; AND Z&#39;&#39; IS H, ALKYL, HYDROXYALKYL, A FLUORINATED ACYL RADICAL RFCO- WHEREIN RF IS AS DESCRIBED ABOVE, A HALOALKANOYL RADICAL OR A RADICAL HAVING THE FORMULA-CXH2XNHZ WHEREIN Z IS AS DESCRIBED ABOVE, THERE BEING AT LEAST ONE FLUORINATED ACYL RADICAL RFCO-AND AT LEAST ONE HALOALKANOYL RADICAL IN THE MOLECULE REPRESENTED BY Z AND /OR Z&#39;&#39;.

United States Patent 3,576,017 HALOALKANOYL DERIVATIVES OF FLUORINATED AMIDES Richard F. Sweeney, Randolph Township, Morris County, and Alsou K. Price, Morris Township, Morris County, N.J., assignors to Allied Chemical Corporation, New York, N.Y. No Drawing. Filed Aug. 1, 1968, Ser. No. 749,321 Int. Cl. C09f 7/00 U.S. Cl. 260-4045 16 Claims ABSTRACT OF THE DISCLOSURE Haloalkanoyl derivatives of fluorinated amides useful as oiland water-repellency agents have the structural formula wherein x and y are integers from 2 to 6 and 1 to 4, respectively; wherein R is a perfluoroalkyl or a fluorinated isoalkoxyalkyl radical; Z is H, alkyl, hydroxyalkyl, a fluorinated acyl radical R CO- wherein R, is as described above, or a haloalkanoyl radical; and Z is H, alkyl, hydroxyalkyl, a fluorinated acyl radical R,CO wherein R; is as described above, a haloalkanoyl radical or a radical having the formula CXH2XNHZ wherein Z is as described above, there being at least one fluorinated acyl radical R CO- and at least one haloalkanoyl radical in the molecule represented by Z and/or Z.

BACKGROUND OF THE INVENTION This invention is directed to a new class of fluorcarbon derivatives and to their application to fibrous materials such as textiles and paper to produce oiland Water-repellent products. More particularly, this invention relates to reaction products of fluorinated polyamide compounds with haloalkanoyl halides, to treatment of textile, paper and other fibrous materials therewith to render the same oleophobic and hydrophobic, and to textile, paper and other fibrous products treated therewith so as to have been rendered oiland water-repellent.

It is known to employ certain fluorochemicals in the treatment of textiles, paper and other fibrous products to impart thereto oiland water-repellency properties. In general, these fluorochemicals are composed of a fluorinated alkyl chain affixed to an active functional group. The oleophobic and hydrophobic properties of the fluorochemicals are attributed, at least in part, to the inherent low surface energy of the fluorinated surface provided by the fluorinated alkyl chain. The portion of the molecule to which the fluorinated alkyl chain is afiixed provides the physical and chemical bond between the fluorinated alkyl chain and the substrate surface. This bond not only influences the degree of orientation and packing of the fluorinated groups of the fluorinated alkyl chain, and hence, the oiland water-repellency properties of the fluorochemical, but in particular, determines the durability of the oleophobic and hydrophobic properties obtained. There is always a need for new oiland water-repellency agents, particularly for those which are not only capable of obtaining high levels of oiland water-repellency, but are also capable of maintaining oleophobic and hydrophobic properties of substrate surfaces treated therewith after their repeated exposure to laundering.

Accordingly, one object of the present invention is the provision of novel fluorocarbon derivatives.

Another object is to provide oiland water-repellent compositions of novel fluorocarbon derivatives suitable for treating fibrous materials, such as paper and textiles, to impart thereto oleophobic and hydrophobic properties.

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A still further object is to provide methods for the treatment of textiles, paper and other fibrous products employing said fluorocarbon derivatives.

A further object is to provide textile and paper materials treated with the fluorocarbon derivatives of the present invention.

These and other objects will be apparent from the following description.

DESCRIPTION OF THE INVENTION In accordance with the present invention, reaction products of fluorinated polyamide compounds with haloalkanoyl halides have been found to impart to textiles, paper and other fibrous products durable oiland water-repellency properties.

The compounds proposed for use as oiland waterrepellency agents conform to the general formula:

( 1) R, is a radical selected from the group consisting of (a) perfluoroalkyl having from 3 to 17 carbon atoms,

and

wherein (i) R and R are fluorine or are fluoroalkyl groups, or, when taken together, are fluoroalkylene groups forming a cycloaliphatic structure, which R and R groups may each have from 1 to 9 carbon atoms, provided that not more than three of the R and R groups may be fluoroalkyl groups,

(ii) m and n are each integers of from 0 to 20, with the proviso that the sum of m and n is from 0 to 20, and provided further that when r is 0, m is at least 1,

(iii) X is selected from the group consisting of hydrogen and fluorine, with the proviso that when n is greater than 0, then X is always hy drogen,

(iv) 1 is 0 or 1,

(v) r is 0 or 1, with the proviso that when the sum of m, n and p is greater than 0, and r is always 0,

(2) x is an integer from 2 to 6, (3) y is an integer from 1 to 4, (4) Z is a member selected from the group consisting of (a) hydrogen,

(b) alkyl having from 1 to 6 carbon atoms,

(c) a radical having the formula ROH wherein R is a divalent alkylene bridging group containing from 1 to 6 carbon atoms,

(d) a fluorinated acyl radical having the formula 0 ffl-Rg wherein R, has the afore-stated meaning, and (e) a haloalkanoyl radical having the formula 0 ll CY wherein Y is a haloalkyl radical having from 1 to 6 carbon atoms containing from 1 to 2 halogen 3 atoms selected from the group consisting of chlorine and bromine, and (5) Z, which may be the same or different in different XH2X N) groups, is a member selected from the group consisting of (a) hydrogen, (b) alkyl having from 1 to 6 carbon atoms, (c) a radical having the formula ROH wherein R has the afore-stated meaning, (d) a fluorinated acyl radical having the formula wherein R has the afore-stated meaning, (e) a haloalkanoyl radical having the formula wherein Y has the afore-stated meaning, and (f) a radical having the formula i CJIn-N-Z wherein x and Z have the afore-stated meanings, with the proviso that at least one of Z or Z is a fluorinated acyl radical or one of Z is a radical having the formula i C1H21NZ wherein Z is a fluorinated acyl radical, and at least one of Z or Z is a haloalkanoyl radical or one of Z is a radical having the formula wherein Z is a haloalkanol radical, said fluorinated acyl radical and haloalkanoyl radical having the afore-stated formulas.

The novel fluorocarbon derivatives of the present invention may be prepared by reacting a fiuorinated polyamide starting material as hereiubelow defined with a haloalkanoyl halide reactant at temperatures between about 0 C. and about 100 C., preferably in the presence of an inert organic solvent.

The haloalkanoyl halide reactant employed in the preparation of the novel fluorocarbon derivatives of the preseut invention is represented by the formula wherein X is a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine, and Y is a haloalkyl radical, straight chain or branched chain, having from 1 to 6 carbon atoms and containing from 1 to 2 halogen atoms independently selected from the group consisting of chlorine and bromine, which halogen atoms may be arranged on the carbon chain in any available position.

The haloalkanoyl halide reactants herein contemplated, as a class, are known compounds which can be prepared by conventional methods known to those skilled in the art. A partial listing of readily available haloalkanoyl halides, or of haloalkanoyl halides based on readily available halogenated aliphatic carboxylic acids, suitable for making compounds of the present invention includes bromoacetyl bromide, chloroacetyl chloride, tat-bromopropionyl bromide, dichloroacetyl chloride, oc-ChlOI'OPI'OPlOIlYl chloride, fl-chloropropionyl chloride, a-bromo-iso-butyryl bromide, chloroacetyl iodide, bromoacetyl bromide, a-bromo-nbutyryl bromide, fltbIQlIlO-Il-Vfllfil'Yl bromide, 8-bromo- 4 iso-valeryl bromide, oz-blOHlO-PIOPiOIlYl bromide, a,fl-dibromopropionyl bromide, and others.

The fiuorinated polyamide reactant suitable for reaction with the above haloalkanoyl halide reactants is characterized by the structural formula:

0 i l" l Rr i N( C X ZXN) y C :Hh-N-M (II) wherein R,, x and y have the afore-stated meanings, M is a member selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having the formula ROH wherein R has the above-stated meaning and a fiuorinated acyl radical having the formula wherein R, has the above-stated meaning; and M, which may be the same or different in different groups, is a member selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, a radical having the formula ROH wherein R has the above-stated meaning, a fluorinated acyl radical having the formula 0 H C'Rf wherein R, has the above-stated meaning, and a radical having the formula wherein x and M have the above-stated meanings, with the proviso that at least one of M or M is a fluorinated acyl radical or one of M is a radical having the formula in which x is as stated above and M is a fluorinated acyl radical, said fluorinated acyl radical having the aforestated formula, and at least one of M or M is hydrogen.

The fluorinated polyamide reactant of Formula II, above, is prepared by reaction of a fiuorinated carboxylic acid having the formula R COOfl wherein R: has the afore-stated meaning, or a derivative thereof, such as an ester, anhydride or acid halide thereof with a polyalkylene polyamine compound corresponding to the general formula NH2( ;H2xl I )Y CXH2XNHQ, (III) wherein x and y have the afore-stated meanings; Q is selected from the group consisting of hydrogen, alkyl having from 1 to 6 carbon atoms, and a radical having the formula ROH wherein R has the afore-stated meaning; and wherein Q is selected from the group consisting of hydrogen, alkyl having from i to 6 carbon atoms, a radical having the formula ROM wherein R has the aforestated meaning, or an aminoalkyl radical having the formula C H NQ wherein at and Q have the afore-stated meanings; there being at least two hydrogen atoms in the molecule represented by Q and/or Q.

The polyalkylene polyamine reactants of Formula III, above, employed in the preparation of the fluorinated polyamide compounds of Formula II, above, as a class, are known compounds. These reactants may be straightchain or branched-chain compounds and may be used in the form of a single compound, as a mixture of isomers or as a mixture of polyamides containing from 3 to 6 nitrogen atoms in the molecule. Specific examples of polyalkylene polyamines employable herein include diethylene triamine, di-n-propylene triamine, di-i-butylene triamine, di-n-hexylene triamine, triethylene tetramine, tri-i-propylene tetramine, tri-n-hexylene tetramine, 4-(2- aminoethyl)-1,4,7-triazaheptane, tetra 11 hexylene pentamine, pentaethylene hexamine, 1-(hydroxyethyl)-1,4,7- triazaheptane, 1 methyl-8-(6-hydroxyhexyl)-1,4,8,12-tetraazadodecane, 1-(6-hydroxyhexyl) 11,16 dimethyl- 1,11,16,21 tetraazaheneicosane, l,7-bis(2-hydroxyethyl)- 1,4,7,10-tetraazadecane, 4-rnethyl-1,4,7,10-tetraazadecane, and l-methyl-1,5,9-triazanonane. These polyalkylene polyamines can be prepared by standard methods known to those skilled in the art. Preferred polyalkylene polyamines are diethylene triamine, dipropylene triamine, triethylene triamine and tetraethylene pentamine since these are the more readily commercially available compounds.

Fluorinated carboxylic acid reactants, above-described, wherein R, is perfluoroalkyl, suitable for reaction with the above polyalkylene polyamine reactants are saturated straight-chain or branched-chain monocarboxylic acids or stated derivatives thereof containing from 4 to 18 carbon atoms in the acid portion of the molecule. Discrete molecular species of the perfluorocarboxylic acid reactants may be used or mixtures of these reactants in various proportions having the indicated carbon chain length may be employed. Illustrative perfluorocarboxylic acid reactants include perfluorobutyric, perfluorocaproic, perfluoro-caprylic, perfluorolauric, perfluoromyristic, perfluoropalmitic, and perfluorostearic acids, as well as various isomeric forms thereof.

Perfluorocarboxylic acid reactants herein contemplated containing up to about ten carbon atoms are readily prepared by the electrochemical fluorination of alkanoic acids in anhydrous hydrogen fluoride with subsequent hydrolysis of the resulting fluorinated acid fluorides, as disclosed in US. Pat. 2,567,011, issued Sept. 4, 1951. Longer chain perfluorocarboxylic acid reactants, i.e. those containing from about 11 to 18 carbon atoms, may be obtained by reaction of perfluoroalkyl iodides with oleum containing about 15% to 45% sulfur trioxide at elevated temperatures followed by hydrolysis of the resulting perfluorocarboxylic acid fluoride, as disclosed in French Pat. 1,343,601 of Oct. 14, 1963.

Fluorinated carboxylic acid reactants, above described, wherein R is a radical having the formula l (l) R:

wherein R and R have the afore-stated meanings, wherein s and t are each integers from to 20, the sum of s and I being at least 1, and wherein E is a halogen selected from the group consisting of Br and I. Telomers of that type and their preparation are described in commonly assigned copending application of Anello et al. entitled, Telomers and Process for the Preparation Thereof, Ser. No. 633,359, filed Apr. 25, 1967 now US. Pat. 3,514,487, the pertinent subject matter of which is hereby incorporated by reference. By way of general description, these telomers are prepared by radical addition reactions of polyfiuoroisoalkoxyalkyl halide telogens of the formula wherein R R and E have the afore-stated meanings, with telomerizable unsaturated compounds. The telomerization reaction may be initiated by heat or by means of a free radical initiating catalyst. The polyfluoroisoalkoxyalkyl halide telogen starting materials may be prepared by reacting a corresponding fluorinated ketone with an ionizable fluoride salt, e.g. CsF, to form a fluorinated organic salt and then reacting the organic salt with a halogen other than fluorine or chlorine and an olefin. Preparation of the telogen starting materials is described in detail in copending applications of Litt et al., Fluorinated Ethers, U.S. Ser. Nos. 492,276 and 513,574, filed Oct. 1, 1965, and Dec. 13, 1965 respectively, now U.S. Pat. 3,453,333 and 3,470,256, respectively the pertinent subject matter of which applications is hereby incorporated by reference.

Fluorinated carboxylic acids of the formula R COOH wherein R has the Formula IV, above, wherein r, n and p are all 0 and wherein m is at least 2 may be prepared by reacting the corresponding telomer represented by general Formula V, above, wherein t is 0 with ICN or (CN) to form the nitrile, followed by hydrolysis of the nitrile in known manner to form the free acid. The reaction between the telomer and the ICN or (CN) to form the nitrile is carried out under superatmospheric pressure above about 20 to 200 atmospheres or more at temperatures in excess of about 300 C., preferably using an excess of the ICN or (CN) reactant. Hydrolysis of the nitrile to form the free acid can be effected by treatment with aqueous mineral acid, such as hydrochloric, phosphoric, or sulfuric acid, at temperatures between about 60 C. and about 125 C.

Fluorinated carboxylic acids of the formula R COOH wherein R has the Formula IV, above, wherein m is at least 1, p and r are both 0 and n is greater than 0 may be prepared by reacting the corresponding telomer represented by Formula V, above, wherein t is greater than 0 with an alkali metal cyanide to form the nitrile, followed by hydrolysis of the nitrile to form the free acid, as described above. The reaction between the telomer and the alkali metal cyanide is preferably carried out in aqueous alcoholic solution at temperatures between about 60 and about 100 C.

Fluorinated carboxylic acids of the formula R COOH wherein R has the Formula IV, above, wherein m is at least 1, r is 0, p is 1 and X is hydrogen can be prepared by reacting the corresponding telomer represented by general Formula V, above, wherein t is at least 1 with S0 to form the corresponding pyrosulfate, or with oleum to form the corresponding hydrosulfate, hydrolysis of the pyrosulfate or the hydrosulfate with aqueous acid to form the corresponding alcohol, followed by oxidation of the alcohol with dichromate, permanganate or strong nitric acid to form the free acid.

Fluorinated carboxylic acids of the formula R COOH wherein R, has the Formula IV, above, wherein m is at least 1, n and r are both 0, p is 1 and X is fluorine can be prepared by reacting a corresponding telomer represented by Formula V, above, wherein Z is O with to form corresponding acid halides and fluoropyrosulfates and hydrolyzing the acid halides and fluoropyrosulfates by refluxing with water to obtain the corresponding free acids. Fluorinated carboxylic acids of the formula R;COOH wherein R has the Formula IV, above, wherein r is 1 and m, n and p are all can be prepared by the same method from polyfluoroisoalkoxyalkyl halide compounds of Formula VI, above.

Fluorinated carboxylic acids of the formula R COOH wherein R, has the Formula IV, above, wherein m is 1 and r, n and p are all 0 can be prepared from polyfluoroisoal-koxyalkyl halide compounds of Formula VI, above, by reacting them With a Grignard reagent to form a magnesium halide adduct, reacting this adduct with CO to form a magnesium halide salt, and then acidifying the salt to obtain the desired acid. The reactions involving the Grignard reagent and the carbon dioxide proceed very rapidly and can be conducted at temperatures considerably below 0 C. Preparation of these acids is described in detail in commonly assigned co-pending application of Litt et al., Fluorinated Ethers, U.S. Ser. No. 492,276, filed Oct. 1, 1965, now US. Pat. 3,453,333 referred to above.

The esters and acid halides of the above-described acids may be prepared from the acids by conventional procedures.

While the telomers of Formula V, above, and the fluorinated carboxylic acid reactants derived therefrom, may be prepared as discrete compounds, they are generally obtained as mixtures of compounds of varying chain length. It is to be understood that both, the individual discrete fiuorinated carboxylic acid reactants as well as their mixtures of compounds of varying chain length are suitable for the preparation of the fiuorinated polyamide compounds employed in the preparation of the compounds of the present invention.

Preparation of above-described acids wherein R; has the Formula IV, above, is described in more detail in commonly assigned copending applications of Anello et al., US. Ser. Nos. 721,115 and 721,117, both filed Apr. 12, 1968, respectively entitled Fluorocarbon Acids and Derivatives and Fluorocarbon Compounds, the perti- 8 purification for reaction with the haloalkanoyl halide reactant, above described, to form the haloalkanoyl derivatives of the present invention. However, if desired, the fluorinated polyamide may be further purified prior to reaction with the haloalkanoyl halide reactant, as by distillation or recrystallization using any commonly employed inert organic solvent such as acetonitrile or chloroform.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel fluorocarbon derivatives of this invention are prepared by reacting the haloalkanoyl halide reactant with the fiuorinated polyamide starting material in a mol proporation of 1 mol of fiuorinated polyamide to about 0.5 to 10, preferably about 0.5 to 4, mols of haloalkanoyl halide. Reaction temperature and time are dependent upon the particular fiuorinated polyamide and haloalkanoyl halide reactants involved. The temperature ranges from about 0 C. to about 100 C. preferably from about 10 C. to about 30 C. The reaction is quite rapid even at low temperatures. Reaction times generally range between about 10 minutes and about 4 hours.

If desired, the reaction may be conducted in the presence of an inert organic solvent. Although the reaction may be carried out under super-atmospheric pressure, it is preferred to conduct the reaction at atmospheric pressure.

Upon completion of the reaction the desired product can be extracted from the reaction mixture using a suitable solvent, such as ether, acetone, acetonitrile and the like, and can be purified, as e.g., by fractional crystallizatron.

The reaction of the fluorinated polyamide starting material with the haloalkanoyl reactant yields as by-product the halide salt of the polyamide starting material, as illustrated by the equation below which shows the reaction of 1,7 bis(perfluorooctanoyl) 1,4,7 triazaheptane with chloroacetyl chloride:

nent subject matter of which applications is hereby incorporated by reference.

The fiuorinated polyamide reactants of Formula II, above, may be prepared by simply mixing the fluorinated 'carboxylic acid reactant with the polyalkylene polyamine starting material of Formula III, above. These reactants may be charged in a molar proportion of 1 mol of polyalkylene polyamine to about 1 to 7 mols of fluorinated carboxylic acid reactant. If desired, the reaction may be carried out in the presence of a suitable inert organic solvent. Suitable reaction temperatures range between about 0 C. to about 200 C. Upon conclusion of the reaction, the desired fluorinated polyamide compound may be recovered from the reaction mixture by methods known to those skilled in the art.

The reaction product, obtained as the result of the reaction of the fluorinated carboxylic acid reactant and the polyalkylene polyamine reactant above described, may comprise a single compound conforming to the above stated structural Formula II, a mixture of isomers thereof or a reaction mass composed of amide products containing two or more amide functions depending upon the polyalkylene polyamine reactant employed, the reactivity of the fluorinated carboxylic acid reactant present, the solubility of the amide product obtained during the reaction in the reaction mixture and the molar propor- In a preferred embodiment the reaction is carried out in an acetone medium. Acetone is a solvent for the starting materials and the desired product, but does not dissolve the by-product salt. Thus, recovery of the desired product is facilitated in that, upon completion of the reaction, the by-product amide salt can be simply removed by filtration of the reaction mixture.

The reaction is preferably carried out in the presence of an acid interceptor, such as sodium bicarbonate, to thereby increase the yield of the desired product and to reduce the amount of by-product amide salt formed in the reaction.

Since the haloalkanoyl halide reactant is decomposed by water, the reaction is preferably carried out under exclusion of water using anhydrous reagents.

The by-product amide salt can be reconverted to the fiuorinated polyamide starting material in known manner by treatment with an appropriate ion exchange resin, or by treatment with an aqueous base, such as aqueous sodium hydroxide.

The alkylene linkage -C H in the novel compounds of the present invention may be a straight-chain or branched-chain group, preferably containing from 2 to 4 carbon atoms.

The R; groups in the novel fluorocarbon derivatives of the present invention represented by Formula I above, may be the same or different. When the Rf group is a perfiuoroalkyl group, it may be straight-chain or branchedchain, preferably containing from 6 to 14 carbon atoms.

l F-C-Rg moiety of R radical of the compounds of the present invention include the following:

l RlCl I(C1H2x- )y xH2XN -Rr (VII) wherein R y and Y have the aforestated meanings and x is an integer from 2 to 4 constitute preferred embodiments of the present invention, those wherein Y is wherein q is an integer from 1 to 6, more preferably from 1 to 3, and wherein hal is a halogen selected from the group consisting of chlorine and bromine being more preferred yet.

A specific class of preferred embodiments of the present invention are compounds according to Formula VII, above, wherein the R radical has the formula wherein m is an integer from 1 to 10, n is an integer from to 10, with proviso that the sum of m and n is from 1 to 10, and wherein X and p have the aforestated meanlugs.

The following examples relate to the preparation of representative compounds of the present invention but are not intended to be limiting on the scope thereof.

EXAMPLE 1 Solid, 1,7-bis(perfiuorooctanoyl) 1,4,7 triazaheptane (4.5 g., 0.005 mol) is dissolved in 60 ml. of acetone, and 0.2 ml. (0.0025 mol) of chloroacetyl chloride is added in one portion. The reaction mixture is vigorously stirred at 1820 C. for a period of 3 hours, and is then filtered to remove the 1,7-bis(perfiuorooctanoyl) 1,4,7 triazaheptane hydrochloride salt which precipitates during the reaction. The clear filtrate is evaporated to dryness and the residue is once recrystallized from acetone to yield 1.5 g. (31% conversion) of the desired 1,7 bis(perfiuorooctanoyl) 4 chloroacetyl 1,4,7 triazaheptane product having the formula A portion of the product is recrystallized from acetonitrile to give an analytical sample, M.P. 125-126 C. Elemental analysis of that sample compares with calculated values for C H N O CIF O as follows:

Calculated (percent): C, 27.2; H, 1.2.5; N, 4.32; Cl, 3.66; F, 58.7. Analysis (percent): C, 26.6; H, 1.23; N, 4.44; Cl, 3.71; F, 55.3.

Assigned structure is confirmed by infrared analysis.

The 1,7-bis(perfiuorooctanoyl) 1,4,7 triazaheptane reactant is prepared as follows:

A solution of 49 grams (0.475 mol) of diethylene triamine in 60 ml. of diethyl ether is placed in a reaction vessel equipped with a dropping funnel, condenser, magnetic stirrer and a calcium chloride drying tube. After chilling the vessel in an ice water bath for a period of about 20 minutes, 34.2 grams (0.079 mol) of n-perfluorooctanoyl chloride is added with stirring to the contents of the vessel during a 30 minute period. After the addition of the n-perfiuorooctanoyl chloride reactant is complete, the ice water bath is removed and the stirring is continued at room temperature for a period of 20 minutes. Thereafter, ml. of an 8% aqueous sodium hydroxide solution is added to the reaction mixture and the stirring is continued for an additional 15 minutes. The resulting gelatinous precipitate is filtered at reduced pressure and washed with water. After air drying the precipitate, a yield of about 30 grams of 1,7-di-n-perfiuorooctanoyl 1,4,7 triazaheptane, a white solid (melting point 9497 C.), having the following structural formula is obtained:

EXAMPLE 2 Example 1 is repeated using 9.0 g. (0.01 mol) of 1,7 bis(perfiuorooctanoyl) 1,4,7 triazaheptane, 0.76 ml. (0.01 mol) of chloroacetyl chloride and ml. of acetone. Before charging the chloroacetyl chloride to the reaction mixture there is suspended in the reaction mixture 3.0 g. (0.036 mol) of sodium bicarbonate. The reaction is allowed to proceed under constant agitation for a 3 hour period at l0l5 C. The reaction mixture is then worked up as described in Example 1 to provide 5.0 g. (54% conversion) of the desired product.

EXAMPLE 3 Example 1 is repeated using 2.12 g. (0.015 mol) of 4-ch1orobutyryl chloride, 27.0 g. (0.03 mol) of 1,7-bis- (perfiuorooctanoyl) 1,4,7 triazaheptane and 375 ml. of acetone to yield 7.0 g. (23% conversion) of 1,7- bis(perfiuorooctanoyl) 4 (4 chlorobutyryl)-1,4,7- triazaheptane product. A portion of that product is recrystallized from acetonitrile to obtain an analytical sample, M.P. 125126 C. Elemental analysis of the analytical sample compares with calculated values for C24H1603N3F30CI as follows:

Calculated (percent): C, 28.82; H, 1.61; N, 4.2; F, 57.0. Analysis (percent): C, 28.3; H, 1.7; N, 4.4; F, 57.3.

Assigned structure is confirmed by infrared analysis.

EXAMPLE 4 Following the procedure set forth in Example 2 there is reacted 1,9 bis(-perfiuorooctanoyl) 1,5,9 triazanonane with chloroacetyl chloride to obtain as product the compound The 1,9-bis(perfiuorooctanoyl) 1,5,9 triazanonane reactant is prepared as follows:

To a solution of 20 grams (0.0467 mol) of methyln-perfiuorooctanoate in 25 ml. of diethyl ether, there is added 3.07 grams (0.0235 mol) of di-n-propylene triarnine. The resulting solution is heated under reflux temperature for a period of 24 hours. After removal of the solvent under reduced pressure, 16.6 grams of a light yellow oil which solidifies in about 30 minutes to give a white sticky solid is obtained. The white sticky solid is recrystallized from acetonitrile to yield 1,9-bis- (perfiuorooctanoyl) 1,5,9 triazanonane (a white powder melting at 84-85 C.) having the following structural formula:

EXAMPLE The 1,10 bis(perfluorooctanoyl) 1,4,7,10 tetrazadecane reactant is prepared as follows:

To a solution of grams (0.047 mol) of methyln-perfluorooctanoate in ml. of diethyl ether, there are added 3.4 grams (0.023 mol) of triethylene tetrarnine. The resulting solution is heated under reflux temperature for a period of 24 hours. After removal of the solvent under reduced pressure, 20 grams of a white sticky solid is obtained which is subsequently recrystallized from acetonitrile. The product of this reaction is 1,10-di-nperfiuorooctanoyl 1,4,7,10 tetrazadecane, a white powder (melting point 89-92 C.) having the following structural formula:

EXAMPLE 6 Following the procedure set forth in Example 1 there is reacted the amide I(OF )2CFO(CF CONHCHzCHzCHzlNfi-Cli Cl with chloroacetyl chloride to obtain as product the compound The amide reactant is prepared in the following manner: To a solution of 24.7 g. (0.05 mol) of (CF CFO(CF COOCH in 25 ml. of diethyl ether there is added 3.07 g. (0.0235 mol) of di-n-propylene triamine. The resulting solution is heated under reflux for a period of 24 hours. After removal of the solvent under reduced pressure there is obtained the crude product which can be purified by recrystallization from acetonitrile.

In manner analogous to that described in the above examples, other compounds illustrative of the present invention can be prepared as follows:

by reaction of 1,13 bis(perfluorooctanoyl)1,4,7,10,13- pentaazatridecane with B-bromobutyryl iodide.

by reaction of 1,7 bis(perfiuorohexanoyl) 1,4,7-trlazaheptane with 5 bromocaproyl bromide.

by reaction of 1,7 bis[perfiuoro(5-methylhexanoyl)1- 1,4,7 triazaheptane with chloroacetyl chloride.

perfluoroheptanoyl] 1,4,7 triazaheptane with 1,2-dichloropropionyl iodide.

by reaction of 1,7 bis(perfiuorotetradecanoyl) 1,4,7- triazaheptane with 4-chlorovaleryl fluoride.

by reaction of 1,7 bis(perfluorohexadecanoyl) 1,4,7- triazaheptane with 1,1-dichloropropionyl chloride.

anoyl)] 1,4,7,10 tetraazadecane with 5,5 dichlorocaproyl chloride.

by reaction of 1,13 bis(perfluorononanoyl) 1,4,7,10,l3- pentaazatridecane with chloroacetyl chloride.

by reaction of 1,13 bis[perfluoro(l3 methyltetradecanoyl)] 1,4,7,l0,13 pentaazatridecane with chloroacetyl chloride.

by reaction of 1,11 bis(perfiuoroctanoyl) 1,6,11- triazaundecane with bromoacetyl bromide.

CF3 O CFa by reaction of 1,10-bis(perfiuorooctanoyl)-4-(2-aminoethyl)-1,4,7,10-tetraazadecane with 2-bromopropionyl bromide.

by reaction of 1,10-bis (perfluorooctanoyl)-4-(2-n-perfiuorooctanamidoethyl)-1,4,7,10-tetraazadecane with 3-bromobutyryl fluoride.

by reaction of 1,7-bis[perfiuoro(3-oXa-4-methylpentanoyl)]-1,4,7-triazaheptane with dibromoacetyl bromide.

yl) -10-(6-hydr0xyhexyl)-1,4,7,10-tetraazadecane with dichloroacetyle chloride.

by reaction of 1,10,13-tris(perfluorooctanoyl)-4-ethyl- 1,4,7,10,IS-pentaazatridecane with fl-bromopropionyl bromide.

by reaction of 1,7-bis[perfluoro(7-oxa-8-methyln0nanoyl)]-1,4,7-triazaheptane with chloroacetyl chloride.

by reaction of 1,7-bis[2,2,3,3-tetrahydroperfluoro(6-oxa-7- methyloctanoyl)]-1,4,7-triazaheptane with chloroacetyl chloride.

t r? CHzCHzNCOHzCl emolum-C-NHoHHZN-CHQOHQN-OHZOHZIILfi-(OF2)6on3 O=CGH2Ol H O by reaction of 1,10-bis(perfluoro0ctanoyl)-4-(2-aminoethyl)-1,4,7,IO-tetrazadecane with chloroacetyl chloride.

by reaction of 1,10-bis[perfluoro(5-oxa-6-methylheptanoyl)] 2-methyl-4-{2-[perfiuoro(5-0Xa-6-rnethylheptanamido)]ethyl}-1,4,7,1()-tetraazadecane with 2-chloropropionyl chloride.

G G-C Hz-CHr-CI'DCI by reaction of 1.7-bis[2,2,3,3-tetrahydroperfluoro(6-oxa-7- methyloctanoyl)1-1.4,7-triazaheptane with a-chloroisobutyryl chloride.

by reaction of 1,10-bis (perfluorooctanoyl)-1,4,7,10-tetraazadecane with 3-chlorobutyryl chloride.

The oiland Water-repellent compounds of the invention 0-0 H C lBr by reaction of 1,1 3-bis [perfiuoro (3 -oxa-4-methylpentanoyl) 4- (6-hydr0xyhexyl)-10-methyl)-l,4,7,10,13penta azatridecane with chlorobromoacetyl fluoride.

are useful in treating paper as well as textiles (fabrics and P fibers) comprised of natural or synthetic fibers including cotton, nylon, wool, polyethylene terephthalate and polyby reaction of 1,9-bis[12-perfluoro(1l-oxa-lZ-methyltridecyl) dodecanoyl] 13-hexyl-1,5,9,13-tetraazatridecane with w-chloroheptanoyl chloride.

acrylonitrile. The fluorocarbon derivatives of the invention are especially useful in the treatment of fabrics and fibers comprised of cellulose and certain cellulosic derivatives which contain cellulosic hydroxyl groups such as cotton, linen, viscose, cupra ammonium rayon, saponified cellulose acetate and salts of cellulose xanthate. The invention is also applicable to the treatment of blends of natural and/ or synthetic fibers in cloth, for example, blends containing polyethylene terephthalate, polyacrylonitrile, nylon, cotton and wool. If desired, auxiliary agents such as those imparting permanent press, crease resistance and softening properties may be applied in conjunction with the fluorocarbon chemicals of the invention. In addition, other materials such as the surfaces of wood, plastics, glass and metals may be treated with solutions containing the fluorocarbon derivatives of the invention to render the same oiland water-repellent.

The fluorocarbon derivatives of the present invention may be applied to the article to be rendered oil-repellent by treating the same with a solution of the repellent and evaporating the solvent. If desired, the treated article may then be cured at an elevated temperature. The concentrar'ion of the fluorocarbon derivative on the treated article generally may vary from about 0.5% to 10%, preferably 1.0% to 4.0%, based on the weight of the article. Since the solvent used in formulating the oiland water-repellent composition functions essentially as a carrier for the fluorocarbon derivative, any organic liquid inert to the article to be treated and inert to the repellent and capable of dissolution of the requisite amount of oiland waterrepellency agent may be employed. Acetone, methyl ethyl ketone, acetonitrile and dimethylformamide are illustrative solvents which may be used in preparing the oiland Water-repellent compositions. Alternatively, aqueous emulsions of the oiland water-repellent may be applied onto the articles to be treated by conventional aqueous application methods.

The solvent may be evaporated by air drying at room temperature. If it is desired to cure the treated articles the solvent may be evaporated prior to curing or during curing of the oiland Water-repellent chemical onto the article. Preferably, the article treated with a solution of the fluorocarbon derivative is air dried prior to curing for a time suflicient to evaporate essentially all of the solvent. Thereafter, the article having on its surface the oiland water-repellent chemical is cured or heat-set at a temperature of about 100 C. to 160 C. for a time period varying inversely with the temperature ranging from about 1 second to 5 minutes.

When cellulosic materials are to be rendered oiland water-repellent, the fluorocarbon derivatives of the present invention are preferably applied thereto from an aqueous solution or an aqueous emulsion and in the presence of a catalyst of the type commonly used as a crosslinking catalyst for crosslinking resins with cellulosic materials. The fluorocarbon derivatives of the present invention respond to basic as Well as acidic catalysts, thus have the decided advantage that their use is compatible with perma nent press treatment, which treatment commonly employs acidic reactants. The cellulosic material is moistened with an aqueous solution of the catalyst, air dried to remove residual water and then impregnated with an aqueous solution or emulsion of the fluorocarbon derivative of the invention for a time, normally 30 seconds to about 30 minutes, suflicient to retain on the cellulosic material about 1 to preferably 2 to 4% of the fluorocarbon derivative, based on the weight of the cellulosic material. The thusly impregnated cellulosic material is then heated at a temperature of 100 C. to 165 C. for a time period varying inversely with the temperature ranging from about minutes to seconds. After the reaction of the fluorocarbon derivative with the cellulosic material is complete, the chemically modified cellulosic material is washed free of excess catalyst with water and dried.

Various modifications of the above-described treatment may also be employed without departing from the spirit of the invention. For example, the cellulosic material may be first impregnated with an aqueous dispersion or emulsion of the fluorocarbon derivative, then treated with an aqueous solution of the catalyst, air dried and finally heated to effect reaction of the fluorocarbon derivative with the cellulosic material. Another modification of the above-described procedure involves premixing the aqueous dispersion or emulsion of the fluorocarbon derivative together with the catalyst prior to impregnation of the cellulosic material. Chemical modification of the cellulosic material under anhydrous conditions, as in the presence of solvents capable of penetrating cellulosic fibers such as benzene, chloroform, dioxane and acetone constitutes still another variation of the afore-described procedures.

In general, suitable basic catalyst should have a disassociation constant in Water of at least l.8 l0 at 25 C. Phosphates, carbonates and hydroxides of alkali metals such as sodium phosphate, sodium carbonate, sodium hydroxide and potassium hydroxide; alkaline-earth metal hydroxide including calcium hydroxide and magnesium hydroxide; and quarternary ammonium hydroxide and benzyl trimethyl ammonium hydroxide are illustrative of preferred effective basic catalysts. Suitable acid catalysts are the mineral acids and strong organic acids, as Well as the ammonium salts, amine salts and metal salts of strong acids. The salts of strong acids are preferred acid catalysts, ammonium chloride, magnesium chloride, zinc nitrate and zinc chloride being specific examples of preferred acid catalysts. The catalyst concentration is normally dependent upon the strength of the acid or base catalyst selected, speed of reaction desired and the nature of the cellulosic material to be treated. In general, catalyst concentrations of about 1 to 20%, preferably 2 to 5%, based on the weight of the solution are satisfactory.

Results of tests relating to the evaluation of typical fluorocarbon derivative compositions of the present invention as oiland water-repellency agent on textiles are shown below.

The procedure employed in determining the oil-repellency ratings on textiles is described, for example, on pages 323-4 of the April 1962 edition of the Textile Research Journal. This procedure involves gently placing on the treated fabric drops of mixtures of mineral oil (Nujol) and n-heptane in varying proportions. The drops are allowed to stand on the treated fabric undis turbed for 3 minutes. After the 3 minute time period the Wetting and penetration of the fabric is visually observed. Referring to following Table I, the number corresponding to the mixture containing the highest percentage of heptane which does not penetrate or wet the fabric is considered to be the oil-repellency rating of the treated fabric.

TABLE I Percent mineral Percent oil I n-heptane Oil-rfpelleney rating:

i Nujol Saybolt viscosity 360;390 at F. Specific gravity 0.880] 0.900 at 60 F. Percent by volume at 20 C.

2 Heptane, B.P. Oil-99 0. Percent by volume at 20 C.

17 tion of Textile Chemists and Colorists which is described, for example, on pages 152-153 of the Technical Manual and Yearbook of that association for the year 1961. It is to be noted that this method provides for no interpolation of results which are reported as one of the Stand- Results of tests relating to the evaluation of typical fluorocarbon derivatives of the present invention as oil-, waterand ink-repellency agent on paper are shown in the following.

All tests were conducted on handsheets formed from ard Spray Test ratings which are the six ratings 0, 50, 50/50 softwood-hardwood bleached kraft pulp beaten to 70, 80, 90 and 100. 400 ml. Canadian Standard freeness, both unsized and in- Wash fastness of the treated cloth was determined by ternally rosin sized. The paper was impregnated by total subjecting the cloth to repeated launderings in hot water immersion in solutions of varying concentrations of the in a household automatic washing machine using a heavy repellent in acetone for a period of 60 seconds. Excess duty detergent, followed by drying in an automatic drier. Solution was removed y blotting With blotting P p and The material was ironed prior to testing. the sheets were dried on a rotary handsheet drier at 115 The results obtained are set forth in 'Tables II and C. for a period of 1.5 minutes. Prior to testing the paper HI below: so treated was conditioned at 50% RH. at 72 F. for a period of at least 72 hours.

The procedure employed in determining the oil-repel- TABLE II lency ratings on paper is described, for example, in a Technical Bulletin issued by the Minnesota Mining and Mang gg oihepeL WateHepeL ufacturing Company, entitled Paper Chemical FC805- ment lency rating lency rating IV. Properties Of Treated Paper-C. Oil Resistance2. Haloalkanoy} Comparative Kit Test. This procedure involves gently derivative: placing on treated paper drops of mixtures of castor oil, fig 7,8 toluene and heptane in varying proportions. The drops A c 140 7 are allowed to stand on the treated paper undisturbed for f, $8 g8 15 seconds. After the 15 second period the wetting and B f 130 5 penetration of the paper is visually observed. Failure is L g8 g8 detected by pronounced darkening caused by penetration. The darkening of even a small fraction of the area under explanatmn fsymblssee Note Table the drop is considered failure. With reference to Table IV,

below, the number corresponding to the mixture containing the highest percentage of heptane which does not penetrate or wet the paper is the Kit Number of the paper TABLE III [Oil repellency aiter launderlngs] Method of Number of launderings treatment123456 101510 Haloalkanoyl derivative:

a A 2 d i B g fluorooctanoyl) 4-(4-chlorobutyryD-1,4,7-triazaheptance.

All tests were conducted using x 80 count cotton print cloth. The specimens w r treated as follows:

(a) The cloth was totally immersed in a 5% aqueous sodium hydroxide solution for 5 minutes, and was then air-dried for 30 minutes. The cloth was then impregnated with the repellent by total immersion in a 4% acetone solution of the repellent for 2 minutes. The cloth was then removed from the acetone solution, excess solution was removed by blotting with blotting paper, and dried at 150 C. for 5 minutes. The cloth was then rinsed in warm water for 5 minutes, and was ironed. Prior to tests the cloth was conditioned at 50% R.H. Ironing and conditioning was repeated after each laundering.

(b) The cloth was impregnated with the repellent by total immersion in a 4% acetone solution of the repellent for 2 minutes. The cloth as then removed from the acetone solution, excess solution was removed by blotting, and the cloth was dried in an oven at 150 C. for 5 minutes. The cloth was then immersed in a 5% aqueous sodium hydroxide solution for 5 minutes, was air dried for 30 minutes, and was then heated in an oven at 150 C. for 5 minutes. The cloth as then rinsed in warm water for 5 minutes, was blotted, was heated to 150 O. for 5 minutes, and was ironed. Prior to tests the cloth was conditioned at 50% R.H. Ironing and conditioning was repeated after each laundering. (e) Same as (b) above, except that a 5% stituted for the 5% sodium hydroxide solution.

aqueous potassium carbonate solution was sub- (d) Same as (b) above, except that water was substituted for the 5% aqueous sodium hydroxide solution.

was repeated after each laundering.

(i) Same as (d), above, except that the cloth was not wrung after impregnation with the repellent, but was blotted with blotting paper instead.

(g) The cloth was immersed in a 4% acetone solution of the repellent for 2 minutes, was wrung, and was cured at 150 C. for 5 minutes. Prior to testing the cloth was rinsed in warm water for 5 minutes. was wrung, dried at C. for 5 minutes, and was ironed and conditioned at 50% R.H. Ironing and conditioning was repeated after each laundering.

(h) Same as (g), above, except that the cloth as not cured, but was instead air-dried overnight.

and is considered to be the oilrepellency rating of the treated paper.

Papers having a Kit Number of or below will exhibit only fair oil-repellency; those papers having a Kit Number of 8 to 10 will have good oil-repellency; and those having a Kit Number of 10 or above will have excellent oil-repellency.

Water-repellency of the treated paper was determined by the so-called Cobb Size mehod, TAPPI Standard T- 441. In this method a weighed specimen of paper is placed under a metal ring of known area. Water is placed in the ring and is allowed to stand on the face of the test paper for 3 minutes. The water is then decanted, the paper specimen is blotted to remove free surface water and is Weighed to determine the amount of Water absorbed. Results are reported in terms of grams of water absorbed per square meter of exposed surface. Papers having a Cobb Size number of 40 to 60 have a fair water-repellency, those having a Cobb Size number of 30 to 40 have good water-repellency, and those having a Cobb Size number of 30 or lower have excellent water-repellency.

The resistance of the treated paper to ink penetration is determined by TAPPI Routine Control Method RC-14. In that method a 1.5 in. square piece of the paper, its edges turned up, is floated on standard writing ink (Schaefiers Skrip Permanent Blue-Black Ink #232 was used in these tests), and the time required for the ink to evenly penetrate to the upper surface of the paper is measured in seconds.

Test results are summarized in Table V, below:

N o'rE:

Specimen A: 1,7,-bis(perfluorooctanoyl)-4-chloroacetyl-1,4,7- triazaheptane applied to unsized handsheets.

Specimen B: 1,7-bis(pertluorooctanoyl)-4-(4-ch1orohutyryl)-1,4,7- triazaheptane applied to unsized handsheets.

Specimen C: 1,7-bis (perfiuorooctanoyl) 4-(4'chl0robutyry1)-1,4,7- riazaheptane applied to internally rosin sized handsheets.

When other haloalkanoyl derivatives within the purview of the present invention are applied to textile and paper materials as described above, similar results are obtained, that is to say a high degree of waterand/ or oil-repellency is imparted to the materials so treated.

Since various changes and modifications may be made in the invention without departing from the spirit thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

20 We claim: 1. Fluorocarbon compounds having the structural formula R( 5l I(C;H2;-l q) -(3xH2;-I'Z wherein (1) R is a radical selected from the group consisting of (a) perfluoroalkyl having from 5 to 15 carbon carbon atoms, and (b) a radical having the formula wherein (i) m an n are integers of from 0 to 5, with the proviso that the sum of m and n is from 0 to 10, and provided further that when r is 0, m is at least 1,

(ii) X is selected from the group consisting of hydrogen and fluorine, with the proviso that when n is greater than 0, then X is always hydrogen,

(iii) p is 0 or 1,

(iv) r is 0 and 1, with the proviso that when the sum of m, n and p is greater than 0,

then r is always 0,

(2) x is an integer from 2 to 4, -(3) y is an integer from 1 to 3,

(4) Z is a member selected from the g1 oup consisting of (a) hydrogen, b) alkyl having 6 carbon atoms, (0) a radical having the formula --ROH where R is a divalent alkylene bridging group containing 6 carbon atoms, (d) a fluorinated acyl radical having the formula wherein R; has the afore-stated meaning, and (e) a haloalkanoyl radical having the formula 0 ll CY wherein Y is a haloalkyl radical having from 1 to 6 car-hon atoms containing from 1 to 2 halogen atoms selected from the group consisting of chlorine and bromine and (5) 2', which may be the same or diiferent in different Z! (C;H2;1 I)- groups, is a member selected from the group consisting of (a) alkyl having from 1 to 2 carbon atoms, (b) a radical having the formula ROH wherein R has the afore-stated meaning, (c) a fluorinated acyl radical having the formula 0 (JRi wherein R; has the afore-stated meaning, (d) a haloalkanoyl radical having the formula 0 ll -o-Y wherein Y has the afore-stated meaning and 21 (e) a radical having the formula XH2X N Z wherein x and Z have the afore-stated meanings, with the proviso that at least one of Z or Z is a fluorinated acyl radical or one of Z is a radical having the formula H xH2xI I-Z wherein Z is a fiuorinated acyl radical, and at least one of Z or Z is a haloal'kanoyl radical or one of Z is a radical having the formula CxH2x -Z wherein Z is a haloalkanoyl radical, said fluorinated acyl radical and haloalkanoyl radical having the aforestated formulas. 2. Compounds according to claim 1 having the structural formula I? l l I Rt-O-N-(QHz-If OXHZN-( JRr O=C-Y wherein R Y, x and y have the meanings given in claim 1.

3. Compounds according to claim 2 wherein R; is a perfluoroalkyl radical having from 6 to 14 carbon atoms. 4. Compounds according to claim 3 wherein Y is -C H hal wherein q is an integer from 1 to 6 and hal is a halogen selected from the group consisting of chlorine and bromine.

5. Compounds according to claim 4 wherein q is an integer from 1 to 3.

6. A compound according to claim 5 having the structural formula 7. A compound according to claim 5 having the structural formula 8. A compound according to claim 5 having the structural formula 9. A compound according to claim 5 having the structural formula 10. A compound according to claim 5 having the structural formula 11. Compounds according to claim 1 having the structural formula wherein y, x and Y have the meanings given in claim 1, and R is a radical having the formula wherein, m, n, r, p and X have the meanings given in claim 1.

12. Compounds according to claim 11 wherein the R, radical has the formula wherein X and p have the meanings given in claim 11, wherein m is an integer from 1 to 5 and n is an integer from 0 to 5, with the proviso that the sum of m and n is from 1 to 10.

13. Compounds according to claim 12 wherein Y is -C H hal wherein q is an integer from 1 to 6 and hal is a halogen selected from the group consisting of chlorine and bromine.

14. Compounds according to claim 13 wherein q is an integer from 1 to 3 and wherein hal is chlorine.

15. A compound according to claim 14 having the structural formula 0 [(C Fa)2C F O-(C Fz) C ONHC2H4]2N-l%-CH2C1 16. A compound according to claim 14 having the structural formula References Cited UNITED STATES PATENTS 2,528,274 10/1950 Gunderson 260-404.5 2,593,737 4/1952 Diesslin et a1. 260-514 2,950,211 8/1960 Huber et a1 260-404.5 3,038,820 6/ 1962 Albrecht 260-404.5 3,420,697 1/ 1969 Sweeney et a1. 260-404.5 3,446,570 5/1969 Sweeney et a1. 260-404.5 3,453,333 7/1969 Litt et a1. 260-633 3,470,256 9/1969 Evans et a1. 260-611 LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl. XJR.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,576,0l7 Dated A -j 1 2 197 Inventor(s) Richard F. Sweeney, Alson R. Price It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 34, "fluorcarbon should be -fluorocarbon--.

Column 3 line 40', "haloalkanol" should be -haloalkanoyl--.

Column 4 3rd formula "M should be --M'--.

Column 4, line 61 "-ROM" should be --ROH- Column 5, line 26, "ro-caprylic" should be --rocaprylic.

Column 5, 2nd formula, "R' should be -R l 0 Column 6, line 24, "Pat." should be Pats..

Column 5 3, line 33, after the word "haloalkanoyl" there should appear the word --halide- Column 11, First formula of Example 6, after 2 delete NC-CH Cl and insert in lieu thereof NH.

Column ll, line 68, after the word "compound" insert the following:

Column 12 the formula following line 10 should read:

Page -2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION t nt o- 17 Dated April 20, 1971 Inventor) Richard F. Sweeney, Alson K. Price PAGE 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

... O O v Column 12, 4th formula, first part of the formula should read:

-- F c CF2 Column 12 line 34 after the "I there should appear Column 14 line 8 "chloroacetyle should read -chloroacetyl--.

Column 16 Table I, under "Oil-repellency rating: "79" should be -70--.

Column 17, in the Note-A: "1,4 ,7-triazaneptanc" should read -l,4- 7-triazaheptane.

Column 17 in the Note.-B: "1,4 ,7-triazaheptance" should read --'l ,4,7tria.zabeptane-.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 576 017 Dated April 20 v 1971 Inventcr(s) Richard F. Sweeney, Alson K. Price PAGE. 3

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 17, in the Note, under section (b) 2nd line, "as" should be '--was-.

Column 17 in the Note, under section (b) 6th line, "as" should be --was-.

Column 17 in the Note, under section (h) lst line, "as" should be was- Column 19 in the Note, under Specimen C: 2nd line a:iazzahoptane" should read -triazaheptane- Column 20, Claim 1, lines 12 through 19 delete the formula and the brackets.

Signed and sealed this 26th day of September 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

